This invention relates to rechargeable electrochemical cells.
The use of non-aqueous electrolytes has allowed the development of high voltage lithium-based electrochemical cells for energy storage. Such cells are further characterised in that their electrodes may be intercalation compounds. The positive electrode structures may be based on transition metal oxides operating at a potential close to 4V vs. Li/Li+. Negative electrode structures of carbons and graphites may be applied, which reversibly intercalate lithium at a potential close to the potential of metallic lithium. Such cells are referred to as lithium-ion cells, as the active lithium is always in its ionic form. Alternatively, alloy negative electrode structures like Li-Al and Li-Sn may be used. Such cells will be referred to as lithium-alloy cells. All of the above configurations provide voltages close to 4V.
For the cells referred to above, one of the limiting factors in terms of energy density has been a low initial capacity retention. In operation, a capacity loss during initial charging of the cells is observed, as is a fading capacity upon extended cycling or storage, which in combination define the initial capacity retention.
These capacity reduction phenomena can be ascribed to the instability of the electrolyte towards the electrodes. Instability towards the negative electrode leads to gassing and formation of a passivating film, whereas instability against the positive electrode leads to corrosion of the electrode structure. Both phenomena involve electrolyte decompositon and result in loss of active lithium and a fading capacity of the cell.
In lithium-ion cells, the losses from the anode reactions dominate the losses at the cathode. The magnitude of the losses merely depends on the type of carbon(s)/graphite(s), the electrolyte and their combination. Using carbon-based anodes, active lithium corresponding to 30-50% of the amount of active lithium in the cell may be lost during the first charge-discharge cycles of the cell, i.e. during the initial charging and the young life of the cell. The use of graphites permits somewhat lower losses in the range 5-30%, however, with poorer long term capacity retention.
In the lithium-ion cell active lithium is provided solely via the cathode. Although prelithiation of carbon/graphite anode structures has been investigated, traditionally lithium-free carbon/graphite structures are applied. Compared to cells based on pure metallic lithium, the loss of active material is quite detrimental. Whereas metallic lithium can be added at 3,800 mAh/g, the specific capacities of the cathode materials are significantly lower.
Currently, active cathode materials are generally selected from LiMn2O4, LiCoO2, LiNiO2, LiNixCo1xe2x88x92xO2, 0 less than x less than 1, these materials having capacities in the range 120-160 mAh/g. Therefore, simply providing additional cathode material to compensate for any loss of active material is relatively inefficient and may reduce the lithium-ion cell capacity and energy density significantly.
Losses also occur in the lithium-alloy cells and in such cells the lithium alloys are generally formed in-situ as this prevents the difficult handling of low potential lithium compounds, e.g. under inert conditions. In such cells active lithium is provided solely via the cathode.
In one type of alloy cell the base material is provided as an oxide. In the case of tin, the reaction scheme is:
4Li+SnO2xe2x86x922Li2O+Sn
4.4Li+Snxe2x86x92Li4.4Sn
The scheme clearly shows the irreversible loss of lithium as lithium oxide which can be in the range of 48% of the total amount of active lithium.
In another type of lithium-alloy cell lithium is simply alloyed into the base metal, such as aluminium, or into a semi-metal, such as silicon, which is applied directly in the cell. In the case of aluminium, the reaction scheme is:
xLi+Alxe2x86x92LixAl
In this case a loss is observed as the diffusion of lithium in the xcex1-phase of the lithium-aluminium alloy is so slow, that lithium therefrom is for practical purposes not released during discharge of the cell. Further, the above instability phenomena still exist and cause additional loss of active lithium.
Accordingly, there is a need for an efficient way of providing additional active lithium to compensate for capacity losses in lithium ion cells as well as in lithium-alloy cells. Such active lithium is provided entirely via the cathode.
A number of patents describes approaches to compensate for the loss of active lithium:
U.S. Pat. No. 4,507,371 and U.S. Pat. No. 5,240,794, both to Technology Finance Corporation, describe lithium manganese oxides with excess lithium compared to LiMn2O4. ""371 describes cathode structures of Li1+xMn2O4, x greater than 0, whereas ""794 describes a range of compositions within the compositional area defined by its corner compositions Li14Mn5O12, Li2Mn3O4, LiMn3O4 and Li4Mn5O12.
U.S. Pat. No. 5,370,710 to Sony describes an approach to alleviating the capacity loss by doping a LiMn2O4 cathode material with an additional amount of lithium to obtain a compound Li1+xMn2O4 either by chemical or electrochemical means. A specific chemical doping method is described in U.S. Pat. No. 5,266,299 to Bell Communication Research, which claims doping of LiMn2O4 or xcex-MnO2 with LiI.
Although a number of approaches exists for the introduction of additional active lithium into rechargeable lithium cells, there is still a need for cathodes of such cells, which provide high capacity, safe and simple processing and which are low cost compounds.
More specifically, an objective of the present invention is to provide rechargeable lithium cells of the lithium-ion or the lithium-alloy type, in which the cathode material has a high capacity, and which can be used for alleviation of the consequences of the capacity loss as well as for subsequent charge-discharge cycling.
The cathode material should display a higher capacity than the capacities of the traditional cathode materials LiMn2O4, LiCoO2, LiNiO2 and LiNixCo1xe2x88x92xO2, 0 less than x less than 1. According to the invention, however, there is no need for the full capacity of the cathode material to be rechargeable. In fact, as the cathode capacity is used for loss compensation as well as for cycling, the fraction used for loss compensation might as well be non-rechargeable. Therefore, whereas the first charge capacity of the cathode material should be higher than for the above prior art materials, the rechargeable capacity does not need to be higher. On the other hand, high rechargeable capacity will not reduce the cell performance.
This objective is accomplished by electrochemical cells, the cathode structure of which comprises a lithium cobalt manganese oxide of a tetragonal structure.
Cobalt manganese oxides and related materials are described in/by:
U.S. Pat. No. 5,084,366 to Matsushita Electric Industrial Co., Ltd., describes a secondary cell, the cathode of which is selected from a group of transition metal oxides including lithium cobalt manganese oxide spinel structures. Such compounds, however, have in their discharged state a chemical composition of LixCoyMn2xe2x88x92yO4, 0.85xe2x89xa6xxe2x89xa61.15 and 0.02xe2x89xa6yxe2x89xa60.3. In their charged state, x reaches a value of 0.7, i.e. the patent does not describe of any compound Li2CoyMn2xe2x88x92yO4, 0 less than y less than 0.6 or its use for compensation of capacity losses.
U.S. Pat. No. 5,506,078 to National Research Council of Canada describes a method of forming a spinel-related xcex-Li2xe2x88x92xMn2O4 upon electrochemical deintercalation of lithium from an orthorhombic LiMnO2 of space group Pmnm and unit cell a=4.572 xc3x85, b=5.757 xc3x85 and c=2.805 xc3x85. Although the patent describes the use of spinel-related structures of composition Li2M2O4, M being a transition metal, it does not describe cobalt manganese oxides such as Li2CoyMn2xe2x88x92yO4, 0 less than y less than 0.6 and the simple handling thereof.
Sxc3xa1nchez et al (J. Electrochem. Soc. 144 (1997) 1939), Guohua et al (J. Electrochem. Soc. 143 (1996) 178) and Liu et al (J. Electrochem. Soc. 143 (1996) 879), all describe lithium cobalt manganese oxides. The compounds described by these groups, however, are included in the compositional range of spinels LixCoyMn2xe2x88x92yO4+xcex4, 0xe2x89xa6xxe2x89xa61, 0.04xe2x89xa6yxe2x89xa60.33, 0xe2x89xa6xcex4xe2x89xa60.5. Thus they do not disclose any information on Li2CoyMn2xe2x88x92yO4, 0 less than y less than 0.6 and it use for the compensation for irreversible losses.
Stoyanova et al (Solid State Ionics 73 (1994) 233-240) describe LiCoyMn1xe2x88x92yO2, 0 less than y less than 0.3 with tetragonal symmetry. The paper further describes the acid delithiation of such compounds, and the subsequent application of the delithiated structures as cathode materials in lithium-metal cells. Thus the concept of the lithium-metal cells which are described differs significantly from the concept of the lithium-ion or lithium alloy cells of the present invention; the cells prepared by Stoyanova et al are assembled in their charged state, while the cells of the present invention are assembled in their discharged state.
Further, as the cells of Stoyanova et al are of the lithium metal type, the paper does not describe the concept of loss compensation.
EP-A-0 778 629 (Kerr-McGee Chemical Corporation) describes the production of compounds of the formula Li2MbMn2xe2x88x92bO4 where M is a metal other than Mn (advantageously Al, Ti, V, Cr, Fe, Co, Ni, Cu). Broadly b can range from 0.001 to 1.999 but when M is Co, b is stated to be advantageously less than 0.2. The materials are suggested as replacements for Li2Mn2O4 in secondary Li ion electrochemical cells. The general disclosure of the patent is quite broad but a product which was partially Li2Co0.2Mn1.8O4 was produced from LiCo0.2Mn1.8O4 by reduction/reaction with LiOH.H2O.
The present invention relates to electrochemical cells of the lithium-ion and lithium-alloy type, the cathode structure of which comprises Li2CoyMn2xe2x88x92yO4, 0 less than y less than 0.6, which has a tetragonal structure derived from the cubic spinel structure.
According to one aspect, the present invention provides a rechargeable electrochemical cell comprising a negative electrode, an electrolyte and a positive electrode, characterised in that the positive electrode structure comprises lithium cobalt manganese oxide of the composition Li2CoyMn2xe2x88x92yO4 where 0 less than y less than 0.6, and one or more rechargeable compounds selected from LiMn2O4, LiCoO2, LiNiO2 and LiNixCo1xe2x88x92xO2, 0 less than x less than 1, preferably LiMn2O4.
According to another aspect the present invention provides a rechargeable electrochemical cell comprising a negative electrode, an electrolyte and a positive electrode, characterised in that the positive electrode structure thereof comprises lithium cobalt manganese oxide of the composition Li2CoyMn2xe2x88x92yO4 where 0 less than y less than 0.6 with an air and moisture insensitive tetragonal structure.
Such cells are preferably based on a non-aqueous electrolyte comprising one or more lithium salts and an anode which comprises an electrochemically active carbon structure selected from the group of graphite, coke and carbon blacks or an alloy based on a metal, in particular aluminium, or based on a semi-metal, in particular silicon, or based on a metal oxide, in particular tin oxide.
Upon first charge of the cell, Li2CoyMn2xe2x88x92yO4, 0 less than y less than 0.6 is able to release a significantly higher amount of lithium compared to the traditionally applied cathode materials. During such initial charging, the structure is changed into a cubic spinel structure, which is comparable to LiMn2O4 in terms of structure and rechargeable capacity. The lithium cobalt manganese oxide simply provides additional non-rechargeable capacity.
The structures of complementary composition, Li2CoyMn2xe2x88x92yO4, y greater than 0.6, have a cubic structure (0.6 less than y less than 1.6) or a trigonal structure (y greater than 1.6). None of these compounds display the spinel structure at any state of charge, and they have cycling properties, which are inferior the those of the spinel or spinel phases.
The cobalt-free material Li2Mn2O4 display structural properties similar to Li2CoyMn2xe2x88x92yO4, 0 less than y less than 0.6, i.e. it has a tetragonal structure, which is changed into a cubic spinel structure upon deintercalation of Li. However, whereas Li2CoyMn2xe2x88x92yO4, 0 less than y less than 0.6 is stable under ambient conditions, Li2Mn2O4 is unstable and the handling thereof requires complex processing, which is not suited for large scale production.
According to the invention the first charge capacity and rechargeable capacity of the cathode material should match the total capacity of the anode and the reversible capacity, respectively.
In one embodiment of the invention the electrochemical cell has a cathode structure, which as the only active compound comprises Li2CoyMn2xe2x88x92yO4, 0 less than y less than 0.6.
In this case optimal matching is obtained from a variation of the cobalt-content of Li2CoyMn2xe2x88x92yO4, 0 less than y less than 0.6. At low y-values, i.e. at low degrees of cobalt-substitution, compounds are obtained which have an initial capacity which is approximately double the rechargeable capacity. At higher y-values compounds are obtained, which have more than double initial capacity compared to rechargeable capacity.
As all of the compounds Li2CoyMn2xe2x88x92yO4, 0 less than y less than 0.6 display high irreversible capacities, cathode structures comprising the lithium cobalt manganese oxide as the only active material are especially adapted to those anode configurations, which display high irreversible loss, traditionally anode structures based on cokes, carbon blacks and alloys like the lithium-tin system.
Table I below summarises the theoretical and actually measured initial capacities of the cathode materials of the present invention. The specific capacities (mAh/g) are measured in half cells with lithium metal negative electrodes at low rate (C/50). They are determined from the amount of charge passed across the cells in the first charge half cycle and the mass of the active material in the cathodes. The initial capacities are obtained upon first charge to 4.7V vs. Li/Li+.
As can be seen from Table I, the first charge capacities of the cathode materials used according to the present invention are significantly higher than the capacity of any of the materials LiMn2O4, LiCoO2, LiNiO2 and LiNixCo1xe2x88x92xO2, 0 less than x less than 1.
Table II below summarises actually measured rechargeable capacities of the materials of the present invention. The specific capacities (mAh/g) are measured in half cells with lithium metal negative electrodes at low rate (C/50). They are determined from the amount of charge passed across the cells in the first discharge half cycle and the mass of the active material in the cathodes. The reversible capacities were measured upon cycling in the potential range 3.5-4.3 V vs. Li/Li+.
As can be seen from Table II, the cathode materials of the present invention display rechargeable capacities, which are lower than the 122 mAh/g of LiMn2O4 but are still applicable for use in practical electrochemical cells.
In one embodiment of the invention the cathode material is Li2CoyMn2xe2x88x92yO4, 0.1 less than y less than 0.5, preferably Li2CoyMn2xe2x88x92yO4, 0.3 less than y less than 0.45, more preferably the cathode material is Li2Co0.4Mn1.6O4.
In a preferred embodiment of the invention the cathode composition comprises rechargeable material in an amount corresponding to 20-98% by weight of the complete electrode structure, respectively, preferably 50-98%, more preferably 70-95% and even more preferably 80-95% by weight of the complete electrode structure.
In an alternative embodiment of the invention the electrochemical cell has a cathode structure, which in addition to Li2CoyMn2xe2x88x92yO4, 0 less than y less than 0.6 comprises one or more rechargeable compounds selected from the group of LiMn2O4, LiCoO2, LiNiO2 and LiNixCo1xe2x88x92xO2, 0 less than x less than 1. In a preferred embodiment the rechargeable material is LiMn2O4.
Such cathode structures are especially applicable in those cases, where a relatively low irreversible loss at the anode should be compensated. In this case the capacity matching is achieved by the choice of composition in terms of cobalt manganese oxide and rechargeable materials. Thus composite structures can be produced, which match a low irreversible loss of e.g. 20%, typical for a graphite based anode. In such case, using Li2Co0.4Mn1.6O4 as representative of Li2CoyMn2xe2x88x92yO4, 0 less than y less than 0.6 and LiMn2O4 as rechargeable material, a cathode composition of Li2Co0.4Mn1.6O4:LiMn2O4=1:3.59 by weight should be applied. Such composition matches the 20% irreversible loss at the anode, as itxe2x80x94per gram of Li2Co0.4Mn1.6O4xe2x80x94provides an irreversible capacity of 227-94 mAh=133 mAh and a rechargeable capacity of 94+3.59xc3x97122 mAh=532 mAh.
Table III below summarises the initial (first charge) capacities of composite cathode structures comprising mixtures corresponding to 1:3.59 combinations (by weight) of the indicated cathode material and LiMn2O4. Table III further compares the initial capacities of composite cathode structures to the weighted sum of components as based on their individual capacities (Table I) and based on an initial capacity of LiMn2O4 of 122 mAh/g.
The 1:3.59 combination by charge used in table III and below in table IV and example 3 and 4 illustrate the preferred cathode composition in the case of approximately 20% irreversible loss at the anode. In such case the reversible and irreversible capacities of the cathode would match the reversible capacity and irreversible loss at the anode. The use of the 1:3.59 by weight combination should not be considered as any limitation on the scope of the invention.
The capacities were measured in half cells with lithium metal negative electrodes at low rate (C/50). They are determined from the amount of charge passed through the cells in the first half cycle and the total amount of oxide in the cathodes structures, i.e. they are specific initial capacities (mAh/g) for the 1:3.59 by weight composite of Li2CoyMn2xe2x88x92yO4, 0 less than y less than 0.6 and LiMn2O4. The initial capacities are obtained upon first charge to 4.7V vs. Li/Li+.
As can be seen from Table III, the first charge capacities of the composite cathode structures of cathode materials of the present invention and LiMn2O4 are significantly higher than the capacity of pure LiMn2O4. As can further be seen from Table III, the actually measured initial capacities of the composite cathode structures are in accordance with the sum of initial capacities of the individual components, weighted by their relative abundance.
Table IV below summarises rechargeable (reversible) capacities of composite cathode structures comprising mixtures corresponding to 1:3.59 combinations (by weight) of the indicated cathode material and LiMn2O4. Table IV further compares the rechargeable capacities of composite cathode structures to the weighted sum of components as based on their individual capacities (Table II) and based on an rechargeable capacity of LiMn2O4 of 122 mAh/g.
The specific capacities (mAh/g) are measured in half cells with lithium metal negative electrodes at low rate (C/50). They are determined from the amount of charge passed across the cells in the first discharge half cycle and the mass of the active material in the cathodes, i.e. they are specific reversible capacities (mAh/g) for the 1:3.59 by weight composite of Li2CoyMn2xe2x88x92yO4, 0 less than y less than 0.6 and LiMn2O4. The reversible capacities were measured upon cycling in the potential range 3.5-4.3 V (vs. Li/Li+).
As can be seen from Table IV, the reversible capacities of the composite cathode structures of cathode materials used according to the present invention and LiMn2O4 are only slightly lower than the capacity of pure LiMn2O4. As can further be seen from Table IV, the actually measured rechargeable capacities of the composite cathode structures are in accordance with the sum of rechargeable capacities of the individual components, weighted by their relative abundance.
In a preferred embodiment of the invention the negative electrode consists of a graphite, a coke, a carbon black or a lithium alloy.
The cathode composition may comprise Li2CoyMn2xe2x88x92yO4, 0 less than y less than 0.6 and one or more compounds selected from the group of LiMn2O4, LiCoO2, LiNiO2 and LiNixCo1xe2x88x92xO2, 0 less than x less than 1 in amounts corresponding to 20-98% and 1-79% by weight of the complete electrode structure, respectively, preferably 40-98% and 1-59% by weight of the complete electrode structure, respectively, more preferably 50-80% and 10-40% by weight of the complete electrode structure, respectively, even more preferably 65-80% and 10-25% by weight of the complete electrode structure, respectively. This structure is particularly applicable in the case where the negative electrode is of coke and/or carbon black.
The cathode composition may alternatively comprise Li2CoyMn2xe2x88x92yO4, 0 less than y less than 0.6 and one or more compounds selected from the group of LiMn2O4, LiCoO2, LiNiO2 and LiNixCo1xe2x88x92xO2, 0 less than x less than 1 in amounts corresponding to 1-79% and 20-98% by weight of the complete electrode structure, respectively, preferably 1-59% and 40-98% by weight of the complete electrode structure, respectively, more preferably 10-50% and 40-80% by weight of the complete electrode structure, respectively, even more preferably 15-30% and 60-75% by weight of the complete electrode structure, respectively. This cathode composition is particularly applicable in the case where the negative electrode is graphite.
In a preferred embodiment of the invention the electrolyte of the electrochemical cell comprises one or more non-aqueous solvents selected from the group of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, xcex3-valerolactone, xcex3-butyrolactone and one or more salts selected from the group of LiCF3SO3, LiAsF6, LiBF4, LiPF6 and LiClO4.
A particular advantage of the present invention is that the cathode material Li2CoyMn2xe2x88x92yO4, 0 less than y less than 0.6, can be provided in air and moisture insensitive tetragonal form. The material of formula Li2Co0.2Mn1.8O4 described in EP-A-0 778 629 referred to above is prepared by reaction of LiCo0.2Mn1.8O4 with LiOH.H2O and hydrazine as a reducing agent in liquid medium and the product is stated to be sensitive to oxygen and water in the air and, for this reason, is to be handled in an inert atmosphere. It has surprisingly been found that use of an alternative synthesis procedure provides Li2CoyMn2xe2x88x92yO4, 0 less than y less than 0.6, in tetragonal form which is air and moisture insensitive.
In order to ensure air and moisture insensitivity, Li2CoyMn2xe2x88x92yO4, 0 less than y less than 0.6 may be prepared by sintering a mixture of at least two solid compounds which together contain lithium, manganese and cobalt in the required ratio. These compounds may be a lithium manganese compound and a lithium cobalt compound although separate lithium, manganese and cobalt compounds or compounds containing any combination of these metals may be used. In principle the solid compound can be any oxide of lithium and/or manganese and/or cobalt or any compound which decomposes into such an oxide on sintering. Examples of compounds which decompose into the corresponding oxide on sintering are hydroxides, carbonates, acetates, nitrates, etc. A particularly advantageous combination of solid compounds is lithium manganese oxide (LiMnO2) and lithium cobalt oxide (LiCoO2).
Sintering can be carried out at any suitable elevated temperature for formation of the Li2CoyMn2xe2x88x92yO4, 0 less than y less than 0.6, preferably 500 to 900xc2x0 C., more preferably 600 to 800xc2x0 C., most preferably about 700xc2x0 C. Sintering may, for example, be carried out in airor under an inert atmosphere such as nitrogen. The solid compounds can advantageously be mixed initially by grinding and the product after sintering can be ground.